Process of producing effervescent baths.



' To all whom itmagi Lnoromn ssnason, or iiinscneanrnn, Ann srnrirnn' were or saunas,

- GERMANY; SAID HALLEE ASSIGNOR 'ro SAID senasou;

PBOQESS' F PRODUCING EFTEBVESCENT BATHSJ.

No Drawing.

Specification of Letters Patent.

Patented @ct; 1'5, 1912.

Application filed October 30, 1806. Serial lilo. 341,241;

Be it lmow-n'that we, LnoroLn Samson, a resident of Hirschgarten, near Berlin, in the-German Empire, and STEPHAN Hnmnn,

aresident of Griinau, near Berlin aforesaid,

both-subjects-of the German Emperor, have invented new and useful Improvements in Processes of Producing Effervescent Baths, of which the following is a specification.

' Our. invention relates to a process of gencrating: oxygen for efiervescing oxygen baths and other purposes.

The process consists in introducing the salts of perboric acid (perborates), and in particular sodium or ammonium perborate, intothe bath water and in decomposing the same by the addition of substances which exert 1 a catalytic action. The" perborates can-be employed alone or mixed with other -1:veroxids,'salts' or acids.

We are aware that eilervescing, oxygen baths have already been prepared by dissolvinghydrogen perozu'd in bath water, and by using substances exerting a catalytic action to liberate the unstable oxygen. The

- employment of hydrogen peroxid, however,

is attended with certain disadvantages (1 Hydrogen peroxid is unstableand does not keep: well; (2) thehydrogen peroxide of commerce are of great volume, and since for-an efiervescingoxygen bath about three liters of hydrogen peroxid are necessary, the sale of suchvoluminous material for single baths is attended with considerable inconvenience; (3) theliberation of the oxygen from" hydrogen peroxid is irregular aud tor bathing purposes is not sufficiently persistent, at first foaming up too vigorously and 'then rapidly subsidmg; These drawbacks: are-avoided by the employment ofperhorate, a salt which is extremely'richin oxygen and keeps well. It is true thatfroin theperborate hydrogen peroxid again forms," but this, owing tothe diificult solu bility ot'ahesalt and to its peculiar chemicalneture, occurs very gradually, If with perborateasubstance which exerts a catalytic action is also present in thebath water, the evolution of 'oxygen-bubbles is not violent and followed by rapid: subsidence, but commences graduallyand continues unintermittingly and regularly. Thus whereas with theme of, hydrogenperoxid a large part oi the active oxygen escapes unused, the em ployment of-perborate enables the oxygen bubbles to be more economically utilized for bathing purposes, since they are not evolved with such violence and so 'more readily find opportunity tosettle on the skin of thebather in the form of a layer,

longer space of time. The reason ofthis to befound inrthe fact that it dissolves relatively slowly and the entire quantity of hydrogen peroxid latent in it is not disengagedat once, smalt'quantities being continuously evolved, which again are always carried away and decomposed by the action of the the catalyzing substance. Since the employment of perborate resultsiu the evolution (whereas when hydrogenperoxidis used the oxygen alone acts in the nascent condition), an essentially more effective action is attained for bathing purposes. For as oxygen is not liberated directly, hydrogen peroxid being first evolved, a-t'wo-fold action is secured: the action of the nascent peroxid of hydrogen and that of the nascent oxygen. Special experiments havealso been conduchad with a view to explaining: why the eifervescence should-be so much more prolonged and'pronounced when perborate is used, than when hydrogen peroxid is em ployed, although the actual quantity of oxygen at disposal is the same in the-two cases. '\It would seem that when the material,

decomposed by, the catalyzer the water is first supersaturated with oxygen. the case of hydrogen peroxid the. oxygen remains in thelatent condition, whereas the pulverulent, diflicultly soluble perborate introduces a large quantityof adhering air intif'the water, which in accordance with well known-physical laws overcome the condition of equilibrium of the supersaturated solution and cause liberation of the, so to say, latent oxygen in the form of bubbles, which exert'the beneficial mechanical action on the-skin of the bather, and are the condition for theescape of the gas, which is inhaled by the bat-her. The essentially more pronounced action of nascent hydrogenper'oxid compared with that of free hydrogen peroxid is'also apoint which must by no means be overlooked. Thus Bonjean, for instance, has shown Eau Oxygne a IEtat Naissanh "0ompt. Bend. de lAcaolm,

and since their evolution occurs over a peculiar-behavior of perborateis probably of hydrogen peroxid inthe 'nascent state whether hydrogen peroxid or perborate, is

(Zea 804mm, vol. 140, p. 51 (2. D. ref. in l lir'oc/zenrisc/ies (x'mz firnlblatlf 1905, p. 595) 1 that 0.29] gram oi hydrogen pcrnxid requisite to sterilize a liter of Seine water whereas only 0.060 gram of the same substance in nascent condition is sutticient to effect the sterilizati n.

The chief action of the baths is that upon the human skin, am: this action is not merely that due to the mechanical friction of the eflervescing bubbles. ut is also an oxidizing, bleaching and mollifying one. This latter action is of especial significance in conjunction with the mechanical one, particularly in diseases of the skin. Thus when instead of hydrogen peroxid perborate is employed, owing to the greater activity of the latter either a relatively smaller quantity thereof will sullice. or the same quantity of hydrogen peroxid latent in the perf borate will produce a considerably more vigorous action than it does in tree hydrogen peroxid. The perhorate can not. it would appear, be replaced with the sainci advantage by the salts of other peracids. Thus the perchlorates in the presence of catalyzers do not liberate active oxygen in etiervescing condition, while the evolution of oxygen by the persulfates and percarhonates is, as experiments prove, too slight and irregular for thepresent purposes.

To liberate nascent oxygen in effervescent condition any catalyzing substance of in organic or organic nature may be employed. for instance, iodid of potassium, chlorid of lime, peroxid of manganese. .etc.; We have found, however, that diflicultly soluble man ganese salts in pulverulent form give particularly good results. Manganese borate (MnB,O for instance, is especially suitable as catalyzer in conjunction with per borate. The manganese borate with the perborate is converted into manganese peroxid and boric acid, which latter converts the. alkaline Inetaborate liberated from the perborate into neutral borax.

The manganese peroxid, the actual efi'ective catalytic substance, is produced in very fine molecular form, quite gradually, by the action of the perborate on the manganese borate. In this respect there is a difference from the action of other manganese salts, such for instance as manganese chlorid,

' which on being brought together with perborate in aqueous solution instantaneously colors the liquid brown owing to the precipitation of coarse flakes of manganese peroxid and causes a violent, rapidly subsiding reaction.

Owing to the very gradual decomposit on of the manganese borate. to the molecular nature of the minute particles of manganese peroxid formed from it. and whi h remain freely suspended and distributed throughout the entire body of bathing water. to the i boric acid liberated, which exercises a retardmg influence on the decomposition of thepcroxid, gradually commencing and i then prolonged, regular, and intense effervescencc is brought about.

iy mingling the manganese borate with boric acid the alkaline reacting metaborate forming from the pcrborate can be further neutralized. An excess of boric acid will tend to still further retard the process of decomposition.

The action of the manganese borate on perborates is a very peculiar one and a dry mixture of the two substances, if dan'rp is carefully avoided, can be kept without decomposition, only liberating oxygen on being moistened. The'said react-ion, especially in the case of dry mixtures ofthe two substances, can therefore be utilized not only for the preparation of oxygen baths, but

' also for other industrial or technical pur-- poses, for instance for the manufactured powders, tablets and the like, which on being placed in water generate oxygen.

In carrying out our invention we may,

for instance, for each liter of water ta-ke' 1.2 grams sodium perborate, and as catalytic agent 0.06 gram manganese borate, or 0.02 gram manganese sulfate, or- 0.05 gram dry blood fibrin.

Instead of the 'perborate which contains the h drogen peroxid in latent condition, hydrogen peroxid direct or sodium peroxid can be employed with'manganese borate. In this case also the fine molecular precipitation of the manganese 'dioxid and the reaction-retarding effect of the boric acid is to be observed.

Having thus described our invention, what we claim as new'and desire to secure by Letters Patent of-the United States is 1. The process ofgenerating oxygen gas only for eliervescing baths which consist in introducing into water a pulverulent and ditficultly soluble perbo-rate having a large quantity of adhering air, in conjunction with a substance exerting a catalytic action.-

2.'The process of generating oxygen for effervescing baths which consists 1n introducing into water a perborate in conjunction with a ditiicultly soluble manganese salt in pulverulent form, and boric acid.

3. The process of generating oxygen, c0nsisting in introducing into watera perborate in conjunction with manganese borate.

4. The process of generating oxygen, consisting in introducing into water a 'perborate in conjunction with manganese borate and boric acid. 1

5. The process of generating oxygen for eii'ervescing baths which consists in introducing into water a diflicultly soluble manganese salt in pulverulentform and a sub- :stance containing oxygen in loosely com bined form. upon which the manganese salt I In testimony whereof We have signed our 10 names to this specification 111 the presence of two subscribing Witnesses.

LEOPOLD SARASON. STEPHAN HALLER.

the said gas.

VVit-nesses IIENRY HAsPER, \Vommun I-IAUPT. 

